Process for producing catalytic material for hydrogenating unsaturated oils and fats to harden them



June 5, 1923. 1,457,835

J P. HARRIS CATALYTIC MATERIAL FOR HYDROGENATING UNSATURATED OILS AND FATSTO HARDEN THEM Filed July 531920 2 Sheets-Sheet l PROCESS FOR PRODUCING June 5, 1923;

Y J. P. HARRIS PROCESS FOR PRODUCING CATALYTIC MATERIAL FOR HYDROGENATING UNSATURATED OILS AND FATS TO HARDEN THEM Filed July 5, 1920 2 Sheets-Sheet 2 li y ESE JOHN P. f/menz/s.

some r. HARRIS, orcniceeo, ILLINOIS, ASSIGNOR TO THE ALLZBRIGHT-NELL 00., or

cn' rcaeo, rumors, A CORPORATION or ILLINOIS.

PROCESS FOR PRODUCING CATALYTIC MATERIAL FOR HYDROGENATING UNSAT- URATED OILS AND FATS 'I'O HARDEN THEM.

Application filed July 3, 1920. Serial No. 393,871.

To all whom it may concern:

Be it known that 1, JOHN P. HARRIS, a citizen of the United States, and a resident of the city of Chicago, in the county of.

Cook and State of Illinois, have invented certain new and useful Improvements in a Process for Producing Catalytic Material for Hydrogenating Unsaturated Oils and Fats to Harden Them; and I do hereby declare that the following is a full, clear, and exact description of the same, reference being had to the accompan ing drawings, and to the numerals of re erence marked thereon, which form a part of this specification.

This invention relates to a process for producing catalytic material for hydrogenating unsaturated oils and fats to harden them.

For this purpose finely divided metals such as nickel or palladium may be employed. Occasionally other metals such as iron or copper are used but ordinarily nickel is employed as it is cheap and much more active than the last mentioned metals.

It has been proposed to employ asa source of finely divided nickel, the organic salts of such metal, for example, the formate, acetate or lactate. One of these salts was mixed with oil and while so mixed the salt was reduced to yield metallic nickel. The oil served to preserve the catalytic properties of the reduced metal.

The temperature of reduction under such conditions of nickel formats and acetate, for exam is, is not less than 250 C. and it is well own that the higher the temperature of reduction the less active the resulting metal Now I have found that it is possible to reduce such salts of nickel at a considerably lower temperature, i. e. 190 to 220 (3., by grinding the salt to a fine powder before mixing it with the oil and then" heating the mixture in an atmosphere of hydrogen in such a way that the gases formed by the decomposition of-the organic salt is continually removed.

a One of the principal objects of the present invention, therefore, is to provide a process for producing finely divided metalshaving a greater catalytic activity than heretofore obtainable.

Another object of the invention is to provide a process for reducing metallic salts of organic acids at a lower temperature than heretofore.

It is also an object of the invention to provide an improved form of apparatus for preparing catalytic materials.

Other and furtherimportant objects and advantages will hereinafter appear.

In the drawings:

Figure 1 is a side elevation partly in sectlon of my improved form of apparatus.

Figure 2 is substantially a plan view of the same, parts being omitted. 2

Figure 3 ice section on the line of Figure 1.

In carrying out my invention the metallic salt of an organic acid such as nickel acetate isground to fine powder in a ball or other mill not shown. If desired the salt may be mixed with an inert comminuting materialsuch as infusorial earth to aid the grinding action, and to absorb metallic soaps which act as poison to the product.

The presence of such inert riiaterial has various advantages, for instance,"it not only aids the grinding but also facilitates the separation of the finely divided reduced nickel by filtration. If desired a small amount of oil may be mixed with the nickel salt prior to grinding to aid in the production of an intimate mixture of oil and salt and to facilitate finer grinding than is otherwise obtainable.

When ground the salt is introduced into a mixing vat 1, into which .oil is admitted so that an intimate mixture of oil and salt may be formed. Conveniently the oil is an unsaturated fatty oil similar to that; to be hardened by the aidv of the completed catalyst so that the mm of reduction is caused not only to o acatalyst but also simultaneously harden a batch of unsaturated oil. For agitating the mixture two propellers 2 and. 3 are provided adapted to be driven in op osite directions from a shaft 4. The propel er 3 is mounted on a solid shaft 5 rotatably mounted within the hollow shaft 6, which carries the propeller 2. The shafts 5 and 6 are provided at their upper ends with bevel pinions 7? and 8, which mesh with opposite sides of a bevel gear 9 se tated in opposite directions. Fast and loose ulleys 10 and 11 are rovided for drivin the shaft 4. P g

When the salt is thoroughly mixed with the oil, valve 12 is opened and the mixture run into a reacting chamber 13.

The oil is then drawn from the bottom of the chamber 13 through valve 16 and pipe,

17 by means of pump 18. From the pump 18 the oil passes through pipe 19, valve 20 and pipe 21 to a coil 22 arranged within a heating chamber 23. From the top of this coil the oil returns by pipe 24. to the upper part of the chamber 13. Ordinarily the temperature of the main body of oil in the chamber 13 is not above 190 C. and that of the oil passing through the coils 22 not greater than 220 C. As the quantity of oil in the coils is small as compared with that in the chamber 13, the average temperature of the oil is not substantially in excess of 190 C.

Hydrogen is introduced into the lower part of the chamber 13 by a pipe 14:, which communicates by valve 25 and pipe 26 with a hollow spider 27 provided with perforations along each of its arms. The hydrogen is allowed to escape from the chamber 13 by means of a purge pipe 15 controlled by a valve 28 so that the gases resulting from the decomposition of nickel acetate may be carried away.

Unless it is desired to simultaneously harden unsaturated oils other non-oxidizing gases such as nitrogen may be used as a purging agent.

With the temperature of the main body of oil not in excess of 190 C. and that passing through the coils below 220 C. the treatment should be continued for not less than 2% to 3 hours.

Frequent samples of the mixture may be withdrawn through pet-cock 29 to ascertain whether the reaction is substantially complete, at which time the mixture is jet black and colloidal.

When the decomposition is complete valve 20 is closed and the oil is pumped through pipe 30, valve 31 and pipe 32 into filter press 33 to separate the reduced nickel from the greater part of the oil. Sufiicient oil, however, adheres to the particles of nickel to prevent their oxidation after removal from the filter press. The catalyst is now ready for use.

Experiments seem to indicate that heating the entire body of oil to 220 C. produces a somewhat deadened catalyst, while on the other hand superior results can be obtained by taking small quantities of oil, heating them for a short time to 220 C. and then returning them to the main body of oil and thereby cooling them again below 200 C. In other words, there is a time factor as well as a temperaturefactor which must be taken into consideration. The present process and apparatus is particularly designed to take advantage of this discovery. 1

I am aware that many changes may be i made, and numerous details of construction varied through a wide range without departing from the principles of this invention, and I therefore do not purpose limiting the patent granted hereon, otherwise than necessitated by the prior art.

I claim as my invention:

1. The method of forming catalytic material which includes grinding a fatty acid salt of nickel with oil, mixing the comminuted salt with further quantities of oil and applying heat to small portions of the mixture to decompose the nickel salt.

2. The method of forming catalytic material which includes mixing a fatty acid salt of nickel with oil, heating small separated ortions of the mixture to decompose the salt and separating the metallic nickel from the oil by filtration.

3. The process of forming catalytic material which includes grinding a mixture of a fatty acid salt of nickel and an inert comminuting material, mixing the comminuted salt with oil. applying heat to the mixture to decompose the nickel salt, washing out undesirable gases by an inert gas, and absorbing metallic soaps and the like by the inert material.

4. The method of forming catalytic material which includes heating an organic acid salt of a metal having catalytic properties suitable for use in hydrogenizing oils and continually removing the carbonaceous gases formed by the decomposition of the salt, said decomposition being mainly produced by a temporary overheating of subdivided portions of the salt.

5. The method of forming catalytic material which includes decomposing an organic acid salt of a metal having catalytic properties suitable for use in hydrogenizing 0115 at a temperature of aproximately 220 C., the temperature of the main portion of the salt being maintained at substantially 190 C.

6. The method of forming catalytic material which includes mixing a fatty acid salt of a metal having catalytic properties suitable for use in hydrogenizing oils with an unsaturated body, and decomposing the salt by temporarily heating small detached portions of the mixture to a temperature of approximately 220 C.

7. The method of forming catalytic material which includes mixing a fatty acid salt of a metal having catalytic properties suitable for use in hydrogenizing oils with an unsaturated body, and decomposing the salt by temporarily heating small detached portions of the mixture to a temperature of approximately220 C. While keeping the main body of the mixture ata tem erature not substantially in excess of 190 8. The method of forming catalytic material which includes mixing a fatty acid salt of a metalhaving catalytic properties suitable for use in hydrogenizing oils with an unsaturated body, and decomposing the salt by temporarily heating small detached portions of the mixture to a temperature of approximately 220 C and continuously returning said superheated portions to the main body of the mixture, which is at substantially the temperature of hydrogenation.

9. The process of forming catalytic material which includes grinding a mixture of a fatty acid salt, of a metal having catalytic properties suitable for use in hydrogenizing oils together with an inert comminuting material, mixing the comminuted salt with oil, and applying heat to the mixture to decompose the salt.

10. The process of forming catalytic mate rial which includes grinding a mixture of a.

fatty acid salt, of a metal having catalytic properties suitable for use in hydrogenizing oils, together with an inert comminuting material, mixing the comminuted salt with oil, and applying heat to the mixture to decompose the salt and thoroughly agitating the mixture whereby metallic soaps and the.

like are absorbed by the inert materials.

11. The method of forming catalytic material which includes mixing a fatty acid salt of a metal having catalytic properties suitable for use in hydrogenizing oils with oil, and heating small separated portions of the mixture for brief periods of time to decompose the salt.

In testimony whereof I have hereunto subscribed my name in the presence of two subscribing witnesses.

JOHN P. HARRIS.

Witnesses:

RIDSDALE ELLIS, Ammrr J. FIRE. 

